Effect of Freeze Crystallization on Quality Properties of Two Endemic Patagonian Berries Juices: Murta (Ugni Molinae) and Arrayan (Luma Apiculata)

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Article Effect of Freeze Crystallization on Quality Properties of Two Endemic Patagonian Berries Juices: Murta (Ugni molinae) and Arrayan (Luma apiculata)

María Guerra-Valle 1,2, Siegried Lillo-Perez 1,3, Guillermo Petzold 1,* and Patricio Orellana-Palma 4,*

1 Laboratory of Cryoconcentration, Department of Food Engineering, Universidad del Bío-Bío, Av. Andrés Bello 720, 3780000 Chillán, Chile; [email protected] (M.G.-V.); [email protected] (S.L.-P.) 2 Doctorado en Ingeniería de Alimentos, Universidad del Bío-Bío, Av. Andrés Bello 720, 3780000 Chillán, Chile 3 Magíster en Ciencias e Ingeniería en Alimentos, Universidad del Bío-Bío, Av. Andrés Bello 720, 3780000 Chillán, Chile 4 Department of Biotechnology, Universidad Tecnológica Metropolitana, Las Palmeras 3360, P.O. Box, 7800003 Ñuñoa, Santiago, Chile * Correspondence: [email protected] (G.P.); [email protected] (P.O.-P.); Tel.: +56-42-2463173 (G.P.); +56-2-27877032 (P.O.-P.)

Abstract: This work studied the effects of centrifugal block freeze crystallization (CBFC) on physicochemical parameters, total phenolic compound content (TPCC), antioxidant activity (AA), and process parameters applied to fresh murta and arrayan juices. In the last cycle, for fresh murta Citation: Guerra-Valle, M.; and arrayan juices, the total soluble solids (TSS) showed values close to 48 and 54 Brix, and TPCC Lillo-Perez, S.; Petzold, G.; exhibited values of approximately 20 and 66 mg gallic acid equivalents/100 grams dry matter (d.m.) Orellana-Palma, P. Effect of Freeze for total polyphenol content, 13 and 25 mg cyanidin-3-glucoside equivalents/100 grams d.m. for Crystallization on Quality Properties total anthocyanin content, and 9 and 17 mg quercetin equivalents/100 grams d.m. for total flavonoid of Two Endemic Patagonian Berries content, respectively. Moreover, the TPCC retention indicated values over 78% for murta juice, Juices: Murta (Ugni molinae) and Arrayan (Luma apiculata). Foods 2021, and 82% for arrayan juice. Similarly, the AA presented an increase over 2.1 times in relation to the 10, 466. https://doi.org/10.3390/ correspondent initial AA value. Thus, the process parameters values were between 69% and 85% foods10020466 for efficiency, 70% and 88% for percentage of concentrate, and 0.72% and 0.88 (kg solutes/kg initial solutes) for solute yield. Therefore, this work provides insight about CBFC on valuable properties in Academic Editors: Asgar Farahnaky, fresh Patagonian berries juices, for future applications in health and industrial scale. Mohsen Gavahian and Mahsa Majzoobi Keywords: freeze crystallization; murta; arrayan; physicochemical properties; bioactive compounds; antioxidant activity; process parameters Received: 25 January 2021 Accepted: 19 February 2021 Published: 20 February 2021 1. Introduction Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in In the last decades, berries have gained a lot of attention due to their attractive published maps and institutional affil- colors, interesting physicochemical properties, and excellent nutritional and organoleptic iations. characteristics. Thus, berries are not only consumed for their physical appearance but also for their countless and positive effects on the consumers’ health, since these fruits have a significant source of micronutrients, phenolic compounds, and antioxidant activity that provide important beneficial effects for human health [1,2]. In this context, Chile has an important diversity of wild and endemic berries due to Copyright: © 2021 by the authors. the different ecosystems of each region, since Chile presents from dry desert climate (North) Licensee MDPI, Basel, Switzerland. to high-intensity rainfall rate and low temperatures (South) [3]. Hence, in southern-central This article is an open access article distributed under the terms and Chile, there are various endemic berries such as maqui (Aristotelia chilensis), calafate (Berberis conditions of the Creative Commons microphylla), Chilean strawberry (Fragaria chiloensis ssp. chiloensis), murta (Ugni molinae), Attribution (CC BY) license (https:// and arrayan (Luma apiculata), and till date, murta and arrayan have been poorly studied. creativecommons.org/licenses/by/ However, these berries have been used since ancient times as food, ingredients, colorants, 4.0/). and/or traditional medicines [4,5], and it opens the possibility of future scientific analysis

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in the fresh fruits and/or the development of studies for commercial exploitation through new processing technologies. Specifically, murta and arrayan are two interesting and exotic berry fruits recognized as “superfruits,” since these fruits present high levels in terms of fiber, vitamins, minerals, nutrients, and phytochemical composition [6]. Murta (also called murtilla, myrtle berry, or mutilla) is a wild Myrtaceae bush, with black/purple color and an intense sweet taste, and it grows from Talca (35◦25036” S, 71◦40018” W, Maule Region, central Chile) to the Palena River (41◦28018” S, 72◦56012” W, Los Lagos Region, southern Chile) [7]. Similarly, arrayan (also called cauchao) is other wild Myrtaceae endemic plant that grows in forests from Valparaíso (33◦03047” S, 71◦38022” W, Valparaiso Region, central Chile) to Aysen (45◦34012” S, 72◦03058” W, Aysen del General Carlos Ibáñez del Campo region, southern Chile). The fruits have nearly globular shape with characteristic aroma [8]. Moreover, these fruits present an important content of phenolic compounds (phenolic acids, anthocyanins, flavonoids, flavonols, and tannins), and thus, it contributes significantly to the high value of antioxidant activity measured for these fruits [9–14]. Therefore, murta and arrayan have excellent potential to be incorporated into the diet for daily consumption, either as fresh fruits or derived products such as yogurt, jams, jellies, purees, and fruit juices [15]. Additionally, different innovations have been adopted in the food industry due to the demands of consumers, every day more interested and aware, for healthy, safe, tasty, and ideal functional foods with low impact on the environment [16]. Furthermore, these innovations can be made at any stage during the food processing, and in recent years, the changes have been observed through the implementation of emerging thermal and non-thermal technologies with the intention to increase the extraction of components, efficiency, percentage of recovery, stability, and preservation of nutritional and organoleptic characteristics in each food product [17–19]. Accordingly, freeze crystallization (FC) has attracted increasing attention as emerging non-thermal technology due to their important implications for the concentration of food solutions. Specifically, FC uses low temperatures to concentrate liquid solutions and it is based on the freezing of the water, and then, the unfrozen solution (cryoconcentrated) is separated from the ice crystals (frozen fraction). Thereby, FC allows increasing the solutes and bioactive compounds in the cryoconcentrated fraction. In turn, FC had a significant energy advantage compared to the traditional concentration technologies, since FC uses only 14% of the total energy used in evaporative concentration [20]. Hence, FC has been positively applied in various liquid foods, presenting an increase in solutes and extraordinary retention of phenolic compounds and antioxidant activity [21–25]. However, to our best knowledge, there are a few studies available about the application of FC on valuable “superfruit” juices [26,27]. Thus, the objective of this study was to evaluate the use of block FC assisted by centrifugation technology on two wild endemic Chilean berry juices (murta and arrayan) in terms of physicochemical properties, process parameters, and quality characteristics.

2. Materials and Methods 2.1. Raw Materials Fresh murta (Ugni molinae) and arrayán (Luma apiculata) were obtained from Valle Exploradores Ltda (46◦37027” S, 72◦40036” W, Puerto Río Tranquilo, XI Región de Aysén, Chile), with standard commercial maturity, i.e., uniform size and color, and without visual damage (injured) or being immature. Thus, the samples were transported in covered insulated boxes at Chillán (XVI Región del Ñuble, Chile) and were kept in a refrigerated chamber until their further analysis.

2.2. Fruit Juice Preparation The fruits were washed with tap water to remove dust and dirt, and then subjected to manual pressure to obtain the juice, and then, the fresh juice was ﬁltered using a nylon Foods 2021, 10, x FOR PEER REVIEW 3 of 13

2.2. Fruit Juice Preparation The fruits were washed with tap water to remove dust and dirt, and then subjected to manual pressure to obtain the juice, and then, the fresh juice was filtered using a nylon cloth (0.8 mm fine-mesh) to separate large fragments such as pulp, seeds, and peels from the liquid. Later, the fresh juice was stored at 4 °C until analysis or processing.

2.3. Freeze Crystallization (FC) The FC process at three cycles was based on the protocol described by Orella- na-Palma et al. [27] (Figure 1). First, the plastic centrifugal tubes with 45 mL of juice were isolated with foamed polystyrene. Then, the tubes with juice were frozen through axial Foods 2021, 10, 466 freezing front propagation in a static freezer3 of (model 14 280, M&S Consul, Sao Paulo, Brazil) overnight at −20 °C. Later, the cryoconcentrated fraction was separated from the ice frac- cloth (0.8 mm fine-mesh) to separate large fragments such as pulp, seeds, and peels from thetion liquid. by Later, centrifugation the fresh juice was stored at(Eppendorf 4 ◦C until analysis or 5430R, processing. Hamburg, Germany) at 20 °C for 20 min at 4000 2.3.rpm, Freeze Crystallizationand thus, (FC) this procedure can be called the first cycle (C1). The cryoconcentrate juice The FC process at three cycles was based on the protocol described by Orellana-Palma etobtained al. [27] (Figure1 ).from First, the C1 plastic was centrifugal collected. tubes with 45 mLSubsequently of juice were isolated , the C1 solution was used as the new feed with foamed polystyrene. Then, the tubes with juice were frozen through axial freezing frontsolution propagation for in a static the freezer second (model 280, (C2) M&S Consul, cycle, Sao Paulo, and Brazil) thus, overnight the C2 solution was used as new feed solu- at −20 ◦C. Later, the cryoconcentrated fraction was separated from the ice fraction by centrifugationtion for (Eppendorf the third 5430R, Hamburg,(C3) cycle. Germany) atAll 20 ◦C the for 20 mincycles at 4000 rpm, were and performed under the same FC procedure thus, this procedure can be called the first cycle (C1). The cryoconcentrate juice obtained from(axial C1 was freezing collected. Subsequently, front the propagation C1 solution was used as at the new−20 feed °C solution and centrifugation conditions). Specifically, for the second (C2) cycle, and thus, the C2 solution was used as new feed solution for thedifferent third (C3) cycle. quality All the cycles properties were performed under such the sameas physicoc FC procedure (axialhemical properties, total phenolic compound freezingcontent, front propagation and antioxidant at −20 ◦C and centrifugation activity conditions). were Specifically, determined different in the cryoconcentrated fraction from quality properties such as physicochemical properties, total phenolic compound content, andC1, antioxidant C2, and activity C3. were determined in the cryoconcentrated fraction from C1, C2, and C3.

FigureFigure 1. Freeze 1. crystallization Freeze procedure crystallization at three centrifugation procedure cycles. at three centrifugation cycles.

2.4. Physicochemical Profile The physicochemical profile in the samples was measured based on the method described by Orellana-Palma et al. [27]. Thus, the TSS content was measured using a digital refractometer (PAL-3, Atago Inc., Tokyo, Japan) with wide range (0–93%), and the results were expressed as Brix. The pH measurements were determined with a digital pH meter (HI-2221, Hanna Instruments, Woonsocket, RI, USA). The total titratable acidity (TTA) (grams of malic acid (MA) per liter of sample, g MA/L) was obtained by titrimetric method. The density (kg/m3) was obtained using a pycnometer at 25 °C. The color properties were evaluated using a colorimeter (CM-5, Konica Minolta, Osaka, Japan), and the results were provided in accordance with CIELab system (L*: darkness-whiteness, a*; greenness-redness axis, and b*: blueness-yellowness axis). The total color difference (ΔE*) was calculated in accordance with Equation (1).

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2.4. Physicochemical Proﬁle The physicochemical proﬁle in the samples was measured based on the method described by Orellana-Palma et al. [27]. Thus, the TSS content was measured using a digital refractometer (PAL-3, Atago Inc., Tokyo, Japan) with wide range (0–93%), and the results were expressed as Brix. The pH measurements were determined with a digital pH meter (HI-2221, Hanna Instruments, Woonsocket, RI, USA). The total titratable acidity (TTA) (grams of malic acid (MA) per liter of sample, g MA/L) was obtained by titrimetric method. The density (kg/m3) was obtained using a pycnometer at 25 ◦C. The color properties were evaluated using a colorimeter (CM-5, Konica Minolta, Osaka, Japan), and the results were provided in accordance with CIELab system (L*: darkness-whiteness, a*; greenness-redness axis, and b*: blueness-yellowness axis). The total color difference (∆E*) was calculated in accordance with Equation (1). q ∗ ∗ ∗2 ∗ ∗2 ∗ ∗2 ∆E = L − L0 + a − a0 + b − b0 , (1)

where ∆E* is the change variation between fresh juices and cryoconcentrated samples. The subscript 0 corresponds to the initial CIELab values in the fresh juice, and L*, a*, and b* are the color properties in each cryoconcentrated sample.

2.5. Determination of Total Phenolic Compound Content (TPCC) TPCC were determined by the total polyphenol content (TPC), total anthocyanin content (TAC), and total ﬂavonoid content (TFC) assays. TPC, TAC, and TFC assays were measured with a spectrophotometer UV/Vis (T70, Oa- sis Scientific Inc., Greenville, SC, USA) based on the method described by Sekizawa et al.[28], Lee et al. [29], and Zhishen et al. [30], where gallic acid (GA), cyanidin-3-glucoside (C3G), and quercetin (Q) were used for the standard curve, respectively, and the results were expressed in mg of GA equivalents (GAE) per grams (g) of dry matter (mg GAE/g d.m.), mg of C3G equivalents per grams (g) of dry matter (mg C3G/g d.m.), and mg of Q equivalents (QE) per grams (g) of dry matter (mg QE/g d.m.), respectively. Additionally, the TPCC retention represents the TPCC retained from the fresh juice in the cryoconcentrated solution. The TPCC retention was determined by Equation (2) [31].

C TPCC TPCC retention (%) = o × c × 100, (2) Cc TPCCo

where Co is the initial TSS; Cc is the TSS at each cycle in the cryoconcentrated fraction; TPCCc is the value of TPC, TAC, and TFC at each cycle; and TPCCo is the initial value of TPC, TAC, and TFC.

2.6. Determination of Antioxidant Activity (AA) Antioxidant activity was determined by means of the 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), ferric reducing antioxidant power (FRAP), and oxygen radical absorbance capacity (ORAC) assays. DPPH, ABTS, and FRAP assays were measured with a spectrophotometer UV/Vis (T70, Oasis Scientiﬁc Inc., Greenville, SC, USA) based on the method described by Zorzi et al. [32], Garzón et al. [33], and Chen et al. [34], respectively. ORAC assay was evaluated based on the method described by Ou et al. [35] with a multimode plate reader (Victor X3, Perkin Elmer, Hamburg, Germany). The absorbance was measured at 485 nm (λexcitation) and at 520 nm (λemission) every 1 min for 60 min. Trolox (T) was used for the standard curve, and the AA assays were expressed as µM Trolox equivalents (TE) per gram (g) of dry matter (µM TE/g d.m.). Foods 2021, 10, 466 5 of 14

2.7. Process Parameters in FC 2.7.1. Efﬁciency (η) η (%) is deﬁned as the solutes in the cryoconcentrated fraction relative to the solutes remaining in the ice fraction. The η (%) was determined by Equation (3).

C − C η (%) = c I ∗ 100%, (3) Cc

where Cc and CI are the TSS at each cycle in the cryoconcentrated and ice fractions, respectively.

2.7.2. Solute Yield (Y) Y (kg solutes/kg initial solutes, kg/kg) represents the relation between the recovered solute mass in the initial solution and cryoconcentrated solution. The Y (kg/kg) was determined by Equation (4). kg m Y = c , (4) kg m0

where mc is the solute mass in the cryoconcentrated fraction and m0 is the initial solute mass.

2.7.3. Percentage of Concentrate (PC) PC (%) represents the weight in the initial sample relative to the weight remaining in the ice fraction. The PC was determined by Equation (5).

W − W PC (%) = 0 i × 100%, (5) W0

where W0 and Wi are the initial and ﬁnal weights in the ice fraction, respectively.

2.8. Statistical Analysis The treatments were conducted in triplicate at ambient temperature (≈22 ◦C), and the results were presented as mean ± standard deviation. One-way analysis of variance (ANOVA) was used to the evaluation of statistical analysis and the treatment means were compared via Fisher’s least signiﬁcant difference (Fisher’s LSD) test at a conﬁdence level of 0.95 (p ≤ 0.05). The data were analyzed through Statgraphics Centurion XVI software (v. 16.2.04, StatPoint Technologies Inc., Warrenton, VA, USA).

3. Results and Discussion 3.1. Physicochemical Characteristics The physicochemical properties in the fruit juices and CBFC-treated juices are shown in Figure2 and Table1. Additionally, the TSS, pH, TTA, and color (L*, a*, b* and ∆E*) values presented signiﬁcant differences when each BFC cycle was compared with their respective fresh juice. The fresh murta juice presented lower physicochemical characteristics values than those indicated by Ah-Hen et al. [36]. However, our results were higher than previous results found in the same fruit juice by Ah-Hen et al. [37]. Moreover, the fresh arrayan juice values were higher than previous values reported by Fuentes et al. [13]. The differences can be connected to the fact that the studies were carried out with fruits from different areas of the Southern Chile, and these zones are characterized by various climatic conditions, equivalent to constant rains and low temperatures throughout the year [38]. Additionally, various factors such as type/time of harvesting, ripening process, and/or the interaction genotype-environment can change the properties of the fruit and juice [39]. FoodsFoods2021 2021,,10 10,, 466 x FOR PEER REVIEW 66 ofof 1413

(a) (b)

FigureFigure 2.2. Total soluble solids (TSS) values values at at each each BFC BFC cycle: cycle: (a ()a murta) murta juice juice and and (b ()b arrayan) arrayan juice. juice. The The bars bars represent represent the thestandard standard deviations. deviations. The Thenumber number on the on thebar baris the is theconcentrat concentrationion index index (CI), (CI), and andCI is CI a isdimensionless a dimensionless number number that thatrep- representsresents the the increase increase in solutes in solutes at each at each BFC BFC cycle cycle (in (inboth both cryoconcentrated cryoconcentrated and and ice fr iceactions) fractions) with with respect respect to the to theinitial initial TSS value (C0) (14.0 Brix for murta juice and 15.1 °Brix for arrayan juice), i.e., CI = Cc/C0, where Cc is the TSS value at each cy- TSS value (C ) (14.0 Brix for murta juice and 15.1 ◦Brix for arrayan juice), i.e., CI = C /C , where C is the TSS value at each cle. 0 c 0 c cycle. First,The pH, independent TTA, and CIELab of fresh (L*, juice, a*, theand TSSb*) values values are showed given anin Table increasing 1. trend with increasingIn terms BFC of cycles pH, the (Figure values2). showed Hence, ina thesignif lasticant cycle, decrease for murta in both juice fresh (Figure murta2a), thejuice ◦ solutes(pH = 3.7) reached and fresh a TSS arrayan valueclose juice to(pH 48.2 = 5.1),Brix, since and the for values arrayan (third juice cycle) (Figure had2b), a thedecrease TSS ◦ valuein 27% was (pH approximately = 2.4) and 25% 54.0 (pHBrix, = 3.8), which in comparison is comparable to the to ancorrespondent increase in 3.4 pH and value 3.6 times,of the ◦ infresh relation juice, to respectively. the initial TSS By values contrast, (14.0 the and fresh 15.1 murtaBrix), juice respectively. and fresh In comparisonarrayan juice with in- previouscreased the studies TTA in values our laboratory, to 2.3 and the 1.6 results for C1, (third 3.1 cycle)and 2.1 presented for C2, and lower 3.8 concentration and 2.6 for C3, in- dexindicating value than an increase those obtained in 224% in and orange 217% juice (in (5.7) the [last40] andcycle) apple in relation juice (3.9) to [the41], initial but higher TTA thanvalues, those respectively. achieved in The calafate opposite juice (3.0)behavior [27], pineapple among pH juice and (3.3) TTA [42 ],values and blueberry has been juice ob- (2.5)served [43 in]. Thevarious variation cryoconcentrated in TSS values food is due liqui tods the such different as calafate and speciﬁc juice [27], characteristics pineapple (pH,juice TTA,[42], and and sapucaia density, among nut cake others) milk [45]. in the The fresh pH juice, and TTA since changes each characteristic have been attributed interacts underto the variouscontinuous forms increases in the cryoconcentration in TSS at each cycl processe, since [44 it]. provokes It is worth an to increase mention in that, the allor- theganic studies acids usedof the the cryoconcentrates, same freezing and causin centrifugationg the opposite conditions. phenomenon between pH and TTAThe values pH, [41]. TTA, and CIELab (L*, a*, and b*) values are given in Table1. InIn termsterms of colorimetric pH, the values CIELab showed parameters a signiﬁcant, the color decrease measurement in both fresh is considered murta juice an (pH = 3.7) and fresh arrayan juice (pH = 5.1), since the values (third cycle) had a decrease indicator of food quality and can also be used indirectly in the analysis of colored com- in 27% (pH = 2.4) and 25% (pH = 3.8), in comparison to the correspondent pH value of ponents contained in fruits, particularly in berries, providing an estimation of antioxi- the fresh juice, respectively. By contrast, the fresh murta juice and fresh arrayan juice dants and polyphenolic compounds [46,47]. increased the TTA values to 2.3 and 1.6 for C1, 3.1 and 2.1 for C2, and 3.8 and 2.6 for C3, Thus, all the samples presented an important change during the cycles, since each indicating an increase in 224% and 217% (in the last cycle) in relation to the initial TTA parameter had significant modifications, and thus, in C3, the L* values decrease from 52 values, respectively. The opposite behavior among pH and TTA values has been observed to 14 CIELab units and from 12 to 0.4 CIELab units, for fresh murta and arrayan juices, in various cryoconcentrated food liquids such as calafate juice [27], pineapple juice [42], which is equivalent to a decrease in 72% and 96%, respectively, signifying that the cry- and sapucaia nut cake milk [45]. The pH and TTA changes have been attributed to the oconcentrated samples were darker than the original juice. However, as cycles advanced, continuous increases in TSS at each cycle, since it provokes an increase in the organic a progressive increase in a* and b* values was observed, with values from 4 to 35 CIELab acids of the cryoconcentrates, causing the opposite phenomenon between pH and TTA valuesunits and [41 ].from 3 to 15 CIELab units, for murta juice, and from 9 to 39 CIELab units and fromIn 1 termsto 33 CIELab of colorimetric units, for CIELab arrayan parameters, juice, respectively, the color indicating measurement that is the considered juices had an a indicatordarkish red of foodcolor quality (most noticeable and can also in bearrayan used indirectlyjuice), and in thus, the analysisthe final of cryoconcentrated colored compo- nentssamples contained presented in fruits,a very particularly dark visual in appearance berries, providing with red an coloration estimation (Figure of antioxidants 3). These andresults polyphenolic suggested compoundsthat the changes [46,47 in]. visual color of fresh juices treated by BFC can be linked to the notable increase in the TSS concentration and total phenolic compound content at each cycle [48]. Additionally, the ΔE* between the samples (fruit juices and

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Table 1. Physicochemical characteristics of the samples.

pH TTA L* a* b* ∆E* Sample Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Fresh juice 3.7 ± 0.0 a 5.1 ± 0.1 a 1.7 ± 0.2 a 1.2 ± 0.0 a 51.9 ± 1.4 a 12.2 ± 0.1 a 3.8 ± 0.8 a 8.7 ± 0.8 a 2.6 ± 0.5a 1.1 ± 0.2 a -- Cycle 1 3.3 ± 0.2 b 4.7 ± 0.2 b 2.3 ± 0.1 b 1.6 ± 0.2 b 40.6 ± 0.7 b 7.5 ± 0.5 b 8.2 ± 0.4b 22.0 ± 0.2 b 5.9 ± 0.1b 14.0 ± 0.2 b 12.5 ± 0.7 a 19.1 ± 0.5 a Cycle 2 2.8 ± 0.1 c 4.2 ± 0.2 c 3.1 ± 0.4 c 2.1 ± 0.1 c 28.2 ± 0.4 c 4.1 ± 0.2 c 14.7 ± 0.4 c 31.0 ± 1.4 c 10.1 ± 0.9c 22.6 ± 1.3 c 27.2 ± 0.9 b 32.0 ± 1.1 b Cycle 3 2.4 ± 0.1 d 3.8 ± 0.0 d 3.8 ± 0.2 d 2.6 ± 0.3 d 14.4 ± 1.4 d 0.4 ± 0.5 d 34.9 ± 0.3 d 38.9 ± 1.2 d 15.1 ± 0.9d 33.4 ± 0.4 d 50.3 ± 1.2 c 45.7 ± 0.7 c a–d: Different superscript letters in the same column indicate signiﬁcant differences (p ≤ 0.05) according to Fisher’s LSD test. L*, a*, b*, and ∆E*, are the darkness-whiteness axis, greenness-redness axis, blueness-yellowness axis, and the total color difference, respectively. Foods 2021, 10, x FOR PEER REVIEW 7 of 13

CBFC-treated juices) specified that the highest ΔE* values were assessed for the final cycle, since the values ranged from 13 to 50 CIELab units and from 19 to 46 CIELab units, Foods 2021, 10, 466 8 of 14 from the first to the third cycle, for murta juice and for arrayan juice, respectively. Spe- cifically, Krapfenbauer et al. [49] defined that a ∆E* ≥ 3.5 CIELab units denote visual dif- ferencesThus, by all the the consumers samples presentedbetween food an importantproducts. Therefore, change during our values the cycles, indicate since that each the parameterhuman eye had can significant perceive modifications,visual differences and thus,between in C3, the the original L* values sample decrease and from each 52 cry- to 14oconcentrated CIELab units sample, and from since 12 to all 0.4 the CIELab ∆E* values units, forwere fresh higher murta than and 13 arrayan CIELab juices, units. which All the is equivalentdata and visual to a decrease color had in 72%similar and trend 96%, respectively,to the results signifying reported thatin various the cryoconcentrated studies on FC samplesapplied to were fresh darker juices than [27,31,43]. the original juice. However, as cycles advanced, a progressive increase in a* and b* values was observed, with values from 4 to 35 CIELab units and fromTable 3 to 15 1. Physicochemical CIELab units, for characteristics murta juice, of andthe samples. from 9 to 39 CIELab units and from 1 to Sam- pH 33 CIELabTTA units, for arrayanL* juice, respectively,a* indicating thatb* the juices had∆E* a darkish red color (most noticeable in arrayan juice), and thus, the final cryoconcentrated samples ple Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan presented a very dark visual appearance with red coloration (Figure3). These results Fresh 3.7 ± 1.7 ± 51.9 ± 3.8 ± 2.6 ± 5.1 ± 0.1 a suggested1.2 that± 0.0 the a changes12.2 in ± visual 0.1 a color of8.7 fresh ± 0.8 juices a treated1.1 ± by 0.2 BFC a can- be linked - to a a a a a juice 0.0 the0.2 notable increase1.4 in the TSS concentration0.8 and total phenolic0.5 compound content at each Cycle 3.3 ± 2.3 ± 40.6 ± 8.2 ± 5.9 ± 14.0 ± 0.2 12.5 ± 19.1 ± 0.5 4.7 ± 0.2 b cycle [481.6]. Additionally,± 0.2 b the7.5∆ E*± 0.5 between b the22.0 samples ± 0.2 b (fruit juices and CBFC-treated juices) 1 0.2 b specified0.1 b that the highest0.7 b ∆E* values0.4 wereb assessed for0.1 theb finalb cycle,0.7 since a thea values Cycle 2.8 ± ranged3.1 ± from 13 to28.2 50 CIELab ± units and14.7 from ± 19 to 4610.1 CIELab ± 22.6 units, ± 1.3 from 27.2 the ± 32.0 first ± to 1.1 the 4.2 ± 0.2 c 2.1 ± 0.1 c 4.1 ± 0.2 c 31.0 ± 1.4 c 2 0.1 c third0.4 c cycle, for murta0.4 juice c and for arrayan0.4 c juice, respectively.0.9c Specifically,c 0.9 Krapfenbauerb b Cycle 2.4 ± et3.8 al. ± [49] defined that14.4 a ±∆ E* ≥ 3.5 CIELab34.9 ± units denote visual15.1 ± differences33.4 ± 0.4 50.3 by the ± 45.7 consumers ± 0.7 3.8 ± 0.0 d 2.6 ± 0.3 d 0.4 ± 0.5 d 38.9 ± 1.2 d 3 0.1 d between0.2 d food products.1.4 d Therefore, our0.3 values d indicate0.9 thatd the humand eye1.2 c can perceivec a–d: Different superscript lettersvisual in differences the same column between indicate the original significant sample differences and each (p ≤ cryoconcentrated 0.05) according to sample,Fisher's LSD since all test. L*, a*, b*, and ∆E*, arethe the ∆darkness-whitenessE* values were higher axis, thangreenness-redn 13 CIELabess units. axis, blueness-yellowness All the data and visual axis, colorand the had total similar color difference, respectively.trend to the results reported in various studies on FC applied to fresh juices [27,31,43].

FigureFigure 3.3. Effect on visual color of fresh murta juice and fresh arrayan juice under centrifugal block freezefreeze crystallizationcrystallization (CBFC): (CBFC): ( a()a) fresh fresh murta murta juice, juice, (b ()b cryoconcentrated) cryoconcentrated murta murta juice, juice, (c) ( freshc) fresh arrayan ar- juice,rayan and juice, (d )and cryoconcentrated (d) cryoconcentrated arrayan arrayan juice. juice.

3.2. Total Phenolic Compound Content (TPCC) The levels of TPCC in the fruit juices and CBFC-treated juices are shown in Table2. Foods 2021, 10, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/foods Foods 2021, 10, 466 9 of 14

Table 2. Total phenolic compound content of fresh juices and cryoconcentrated samples.

TPC TAC TFC Sample (mg GAE/g d.m.) (mg C3G/g d.m.) (mg QE/g d.m.) Murta Arrayan Murta Arrayan Murta Arrayan Fresh juice 6.4 ± 0.8 a 20.5 ± 2.1 a 4.2 ± 0.1 a 8.2 ± 0.9 a 3.2 ± 0.0 a 6.0 ± 0.2 a Cycle 1 8.1 ± 0.2 b 28.7 ± 1.1 b 5.1 ± 0.9 b 10.5 ± 0.5 b 3.6 ± 0.1 b 6.9 ± 0.2 b TPCC retention (%) 70.0 ± 2.1 A 76.9 ± 0.5 A 66.6 ± 1.0 A 70.8 ± 0.6 A 62.1 ± 0.9 A 63.2 ± 0.1 A Cycle 2 13.4 ± 1.0 c 47.0 ± 2.9 c 8.3 ± 1.3 c 17.0 ± 2.0 c 5.8 ± 0.4 c 11.4 ± 1.4 c TPCC retention (%) 78.6 ± 0.9 B 85.9 ± 1.2 B 73.1 ± 1.4 B 77.9 ± 1.1 B 67.8 ± 1.3 B 71.1 ± 2.9 B Cycle 3 19.9 ± 1.2 d 65.6 ± 3.8 d 12.5 ± 1.7 d 24.8 ± 1.7 d 8.6 ± 0.9 d 17.0 ± 2.3 d TPCC retention (%) 91.1± 1.5 C 93.1 ± 0.2 C 85.6 ± 2.0 C 88.0 ± 0.7 C 78.1 ± 2.4 C 82.5 ± 1.2 C a–d: Different small letters in the same column indicate significant differences (p ≤ 0.05) between the fresh juice and their cycles, according to Fisher’s LSD test. A–D: Different capital letters in the same column indicate significant differences (p ≤ 0.05) between the TPCC retention at each cycle, according to Fisher’s LSD test. TPCC, TPC, TAC, and TFC, are the total phenolic compound content, total polyphenol content, total anthocyanin content, and total flavonoid content, respectively.

First, fresh murta juice had TPCC values close to 6.4 mg GAE/g d.m., 4.2 mg C3G/g d.m., and 3.2 mg QE/g d.m., while fresh arrayan juice had TPCC values of approximately 20.5 mg GAE/g d.m., 8.2 mg C3G/g d.m., and 6.0 mg QE/g d.m., for TPC, TAC, and TAC, respectively. These results were lower than the ones reported by Ramirez [50], who reported the phenolic compounds content profile of six small berries from the VIII Region del Bio-Bío of Chile. However, the differences in TBCC values between the studies might be explained by the different harvest areas, since the VIII Region del Bio-Bío has dry temperate climates in summer and rainy temperate climates in winter, and thus, the temperature varies from 0 to 30 ◦C throughout the year, while the Southern Chile has constant rains and low temperatures throughout the year [38,51,52]. Hence, the climatic conditions and geographical characteristics contribute to various differences on fruit maturation, and in addition, other factors such as genetic and species variabilities, harvesting year, and growing season affect the phenolic compounds content in final fruits [53]. Concerning TPCC results, a similar behavior to the TSS values was observed, since a significant increase in TPC, TAC, and TFC values was detected as cycles advanced. Thus, in the last cycle, for murta juice, the values were close to 20.0 mg GAE/g d.m., 12.5 mg C3G/g d.m., and 8.6 mg QE/g d.m., and for arrayan juice, the values were approximately 65.6 mg GAE/g d.m., 24.8 mg C3G/g d.m., and 17.0 mg QE/g d.m., for the first, second, and third cycle, respectively, and thus, these values were over 2.7 times higher than the correspondent initial TPCC value. This upward trend in TPCC values post-FC has been observed in numerous food liquids such as green tea extract [21], fruit juices [22–24], broccoli extract [25], coffee extract [54], and wine [55]. Additionally, the retention specified a high amount of TPCC in the cryoconcentrated fraction, since the retention values (third cycle) were close to 91%, 86%, and 78%, for murta juice, and 93%, 88%, and 82%, for arrayan juice, for TPC, TAC, and TFC, respectively. The results were consistent with the values informed by Orellana-Palma et al. [41], Casas-Forero et al. [31], and Correa et al. [56], who reported TPCC retention close to 85%, 71–91%, and 90%, in apple juice, blueberry juice, and coffee extract, respectively. Therefore, the TPCC value and retention results allow corroborating that the FC technology can be visualized as a novel alternative due to the low temperatures used to concentrate, preserve, and retain an endless number of phenolic components such as polyphenols, anthocyanins, and flavonoids in the cryoconcentrated fraction [20].

3.3. Antioxidant Activity (AA) Table3 shows the AA values of the samples. Foods 2021, 10, 466 10 of 14

Table 3. Antioxidant activity (µM TE/g d.m.) of fresh juices and cryoconcentrated samples.

DPPH ABTS FRAP ORAC Sample Murta Arrayan Murta Arrayan Murta Arrayan Murta Arrayan Fresh juice 33.4 ± 3.7 a 62.0 ± 7.4 a 48.1 ± 7.6 a 84.8 ± 9.9 a 62.6 ± 5.9 a 92.6 ± 3.1 a 21.7 ± 3.0 a 43.4 ± 4.4 a Cycle 1 96.9 ± 10.1 b 167.3 ± 11.6 b 110.6 ± 19.1 b 229.0 ± 10.4 b 156.5 ± 15.7 b 287.0 ± 17.2 b 45.6 ± 7.4 b 99.8 ± 11.7 b Cycle 2 120.2 ± 8.5 c 266.4 ± 20.3 c 187.6 ± 10.7 c 373.1 ± 20.5 c 256.7 ± 13.9 c 416.6 ± 20.7 c 80.3 ± 5.9 c 204.0 ± 17.0 c Cycle 3 157.0 ± 12.3 d 353.1 ± 14.0 d 250.1 ± 17.2 d 407.0 ± 7.6 d 338.0 ± 21.4 d 509.1 ± 23.1 d 108.5 ± 10.1 d 221.3 ± 20.5 d a–d: Different superscript letters in the same column indicate signiﬁcant differences (p ≤ 0.05) according to Fisher’s LSD test.

First, in both murta and arrayan juices, the AA values (µM TE/g d.m.) were approximately 33.4, 48.1, 62.6, and 21.7, and 62.0, 84.8, 92.6, and 43.4, for DPPH, ABTS, FRAP, and ORAC, respectively. These values were lower than those found by Ramirez et al. [48], Augusto et al. [57], and Rodríguez et al. [58], who studied some quality properties of native berries species from different regions of Chile, explicating that the high variability in AA values can be justiﬁed by the interaction of factors such as edaphoclimatic conditions (climate, light, temperature, and other conditions), geographical zone, cultivar/genotype, harvesting period, cultivation practice, fruit maturation, type of storage, and even, the type of juice extraction from the fruit [59]. Foods 2021, 10, x FOR PEER REVIEW Once the fruit juices were subjected to three CBFC cycles, an important increase10 of in13 the AA values (µM TE/g d.m.) was detected, with AA values from 96.9 to 157.0 and from 167.3 to 353.1, for DPPH, from 110.6 to 250.1 and from 229.0 to 407.0, for ABTS, from 156.5 to 338.0 and from 287.0 to 590.1, for FRAP, and from 45.6 to 108.5 and from 99.8 to 221.3, forand ORAC, later, in from the theseparation C1 to C3, process, for murta these juice, components and for arrayan can facilitate juice, which or complicate is equivalent the toextraction an increase of cryoconcentrates over 2.1, 2.5, 2.7, from and the 2.8 ice times, fraction in comparison [63]. to the AA values from the freshThe juices, Y parameter respectively. (Figure In this 4b) way, showed Orellana-Palma a significant etincreasing al. [27], Samsuri trend as et the al. cycles [60], and ad- Casas-Forerovanced, with etvalues al. [61 of] alsoapproximately observed higher 0.72, AA0.75, values and 0.79 post-FC (kg solutes/kg than the original initial solutes), sample, demonstratingfor murta juice, the and positive 0.82, 0.85, effects and of 0.88 the (kg FC solutes/kg on TPCC, andinitial in turn,solutes), these for components arrayan juice, allow for concentratingthe C1, C2, and and C3, preserving respectively. the antioxidant The result activitys had comparable from the fresh performance juice [21]. that prior studies [40,41,62], associating the Y values with the recovered mass from the original 3.4.mass, Process i.e., for Parameters each applied cycle, a high quantity of mass can be extracted and collected as a cryoconcentratedThe η, PC, and sample Y results [64]. at each cycle are presented on Figure4.

Figure 4. Process parameters at each CBFCCBFC cycle:cycle: (a)) efﬁciencyefficiency andand percentagepercentage ofof concentrateconcentrate andand ((bb)) solutesolute yield.yield.

4. ConclusionsThe η (Figure 4a) showed a signiﬁcant decreasing trend from C1 to C3, with values close to 76%, 72%, and 69%, and 85%, 83%, and 79%, for murta juice and for arrayan The application of CBFC allowed obtaining higher solutes than the original sample, juice, respectively. The results have similar ranges established by Bastías-Montes et al. [26], with an intensification of the natural color of the fresh juices, leading to increase in the Orellana-Palma et al. [41], and Zielinski et al. [62], who studied the effect of FC in various phenolic compounds and antioxidant capacity in the cryoconcentrates samples, since the TPCC and AA results were over 2.7 and 2.1 times higher than the correspondent initial values, respectively. Moreover, the centrifugation improves the possibility to efficiently extract more cryoconcentrate from the ice fraction due to the high values in , PC, and Y. These data suggest that FC can effectively improve the quality properties as well as visual appearance in any fruit juices. Thereby, the FC creates a unique opportunity for food industry, since this novel emerging non-thermal technology concentrates at low temperatures, and thus, various characteristics from the fresh juice can be retained in the final concentrated product. Therefore, the next challenge could be linked to FC in the production of concentrated juice rich in phenolic components and high antioxidant capacity from endemic fruits at pilot plant scale, and then at industrial scale, and in addition, the cryoconcentrated samples could be studied with a nutritional perspective.

Foods 2021, 10, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/foods Foods 2021, 10, 466 11 of 14

liquid samples, specifying that the η can be related to the TSS values. Specifically, the decrease in η values can be related to the continuous increase in TSS values in the feed solution at each cycle, since the viscosity increases as the solutes increase, and thus, the flow of solutes was slowed in the third cycle than in the previous cycles, causing a difficulty in the separation process. In addition, the high viscosity reduces the ice purity postcentrifugation (increase in TSS values in the ice fractions cycle to cycle) [43]. The PC (Figure4a) displayed an increasing tendency as the cycles passed, with values from 70% to 81%, for murta juice, and from 78% to 88%, for arrayan juice, from the C1 to C3, respectively. The values were similar to those reported in other samples [22,40,62], suggesting that the PC values can be connected to the components in the fresh juice, since each juice has multiple components that interact differently in the FC process, and later, in the separation process, these components can facilitate or complicate the extraction of cryoconcentrates from the ice fraction [63]. The Y parameter (Figure4b) showed a significant increasing trend as the cycles advanced, with values of approximately 0.72, 0.75, and 0.79 (kg solutes/kg initial solutes), for murta juice, and 0.82, 0.85, and 0.88 (kg solutes/kg initial solutes), for arrayan juice, for the C1, C2, and C3, respectively. The results had comparable performance that prior studies [40,41,62], associating the Y values with the recovered mass from the original mass, i.e., for each applied cycle, a high quantity of mass can be extracted and collected as a cryoconcentrated sample [64].

4. Conclusions The application of CBFC allowed obtaining higher solutes than the original sample, with an intensification of the natural color of the fresh juices, leading to increase in the phenolic compounds and antioxidant capacity in the cryoconcentrates samples, since the TPCC and AA results were over 2.7 and 2.1 times higher than the correspondent initial values, respectively. Moreover, the centrifugation improves the possibility to efficiently extract more cryoconcentrate from the ice fraction due to the high values in η, PC, and Y. These data suggest that FC can effectively improve the quality properties as well as visual appearance in any fruit juices. Thereby, the FC creates a unique opportunity for food industry, since this novel emerging non-thermal technology concentrates at low temperatures, and thus, various characteristics from the fresh juice can be retained in the final concentrated product. Therefore, the next challenge could be linked to FC in the production of concentrated juice rich in phenolic components and high antioxidant capacity from endemic fruits at pilot plant scale, and then at industrial scale, and in addition, the cryoconcentrated samples could be studied with a nutritional perspective.

Author Contributions: Conceptualization, M.G.-V., S.L.-P., P.O.-P., and G.P.; methodology, M.G.-V., S.L.-P., and P.O.-P.; software, M.G.-V., S.L.-P., and P.O.-P.; validation, M.G.-V. and S.L.-P.; formal analysis, M.G.-V., P.O.-P., and G.P.; investigation, M.G.-V., S.L.-P., and P.O.-P.; resources, P.O.-P. and G.P.; data curation, M.G.-V. and S.L.-P.; writing—original draft preparation, M.G.-V., S.L.-P., and P.O.-P.; writing—review and editing, P.O.-P. and G.P.; visualization, P.O.-P. and G.P.; supervision, P.O.-P. and G.P.; project administration, P.O.-P.; funding acquisition, P.O.-P. All authors have read and agreed to the published version of the manuscript. Funding: This research was supported by ANID-Chile (Agencia Nacional de Investigación y Desar- rollo de Chile) through the FONDECYT Postdoctoral Grant 2019 (Folio 3190420). Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: Not applicable. Acknowledgments: P.O.-P. acknowledges the ﬁnancial support of ANID-Chile (Agencia Nacional de Investigación y Desarrollo de Chile) through the FONDECYT Postdoctoral Grant 2019 (Folio 3190420). M.G.-V. thanks at the Universidad del Bío-Bío for the doctoral scholarship (2018–2022) and for the “Beca de Investigación.” Foods 2021, 10, 466 12 of 14

Conﬂicts of Interest: The authors declare no conﬂict of interest.

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